Enhanced oil recovery by in-situ steam generation

ABSTRACT

Embodiments of the invention provide methods and composition for stimulating a hydrocarbon-bearing, heavy oil containing formation, a deep oil reservoir, or a tight oil reservoir, whereby exothermic reactants are utilized to generate in-situ steam and nitrogen gas downhole in the formation or the reservoir as an enhanced oil recovery process. An oil well stimulation method is provided, which includes injecting, into the one of the formation and the reservoir, an aqueous composition including an ammonium containing compound and a nitrite containing compound. The method further includes injecting, into the one of the formation and the reservoir, an activator. The activator initiates a reaction between the ammonium containing compound and the nitrite containing compound, such that the reaction generates steam and nitrogen gas, increasing localized pressure and improving oil mobility, in the one of the formation and the reservoir, thereby enhancing oil recovery from the one of the formation and the reservoir.

RELATED APPLICATION

This application is related to, and claims priority to, U.S. ProvisionalPatent Application Ser. No. 61/652,359, filed on May 29, 2012, thedisclosure of which is incorporated by reference in its entirety.

BACKGROUND

Field of the Invention

Embodiments of the invention generally relate to oil well stimulationand compositions for the stimulation of hydrocarbon bearing, heavy oilcontaining formations, deep oil reservoirs, and tight oil reservoirs.More particularly, embodiments of the invention relate to enhanced oilrecovery methods and compositions for stimulating a hydrocarbon-bearing,heavy oil containing formation, a deep oil reservoir, or a tight oilreservoir, whereby exothermic reactants are utilized to generate in-situsteam and nitrogen gas downhole in the formation or the reservoir as anenhanced oil recovery process.

Description of the Related Art

The recovery of unconventional hydrocarbons such as heavy oil isreceiving great interest, as world energy demand increases along withglobal oil prices. Producing such high viscosity oil is complex andchallenging, and usually requires chemical or thermal techniques.

One commonly employed technique for increasing the extraction of heavyoil from the oil reservoir is steam injection. Steam injection isconsidered an enhanced oil recovery process that uses thermal energy tostimulate the oil reservoir. Examples of conventional steam injectionprocesses include, for example, cyclic steam stimulation and steamflooding.

Conventional cyclic steam stimulation includes three stages: injection,soaking. and production. Steam is first injected into the well for aspecified amount of time to heat the oil in the surrounding reservoir tofacilitate the flow of the oil. After injecting a specified amount ofsteam, the injected steam remains in the reservoir to “soak” for anotherspecified amount of time (e.g., typically a few days). The “soaking”steam generates increased pressure in the reservoir, forcing oil to flowfrom the well. Subsequently, oil is produced from the well usingartificial lift (e.g., mechanical extraction of the oil from thereservoir).

Steam flooding is another conventional steam injection process, wherebythe heavy oil in the reservoir is heated to high temperatures todecrease the viscosity of the oil, causing the oil to more easily flowthrough the formation toward the producing wells. Conventional steamflooding relies on constructing a steam generating plant and injectingsteam at a well head. Disadvantages of conventional steam floodingsystems include high initial capital costs (e.g., associated with thesteam generating plant), high operational cost, and heat loss due todistance from generators to downhole, which make conventional steaminjection processes ineffective for recovering oil from deep oilreservoirs. Moreover, existing steam flooding systems are applicable foroff-shore oil reservoirs, and are inapplicable for off-shore ones.

Because conventional steam injection processes have limited effect forstimulating hydrocarbons from deep heavy oil containing formations,off-shore formations or tight oil reservoirs with high operational cost,what is needed are enhanced oil recovery methods and compositions forthe thermal recovery of hydrocarbons from deep heavy oil formations,off-shore, on-shore or from a tight oil reservoir, which require lessinitial capital costs and minimize the operational cost and heat loss inpipelines that are commonly present with conventional steam floodingprocesses.

SUMMARY

Generally, embodiments of the invention provide methods and compositionsfor stimulating hydrocarbon production from hydrocarbon-bearing heavyoil or reservoir oil by generating in-situ steam and nitrogen gasdownhole in a heavy oil formation, a deep oil reservoir, or a tight oilreservoir.

In particular, embodiments of the invention are directed to methods andcompositions that generate in-situ steam and nitrogen gas downhole in aheavy oil formation, a deep oil reservoir, or a tight oil reservoir toimprove oil mobility for enhancing oil production. For example, variousembodiments of the invention provide methods for injectingexothermic-reaction components that react downhole in the heavy oilformation, the deep oil reservoir, or the tight oil reservoir togenerate the in-situ steam (e.g., heat) and nitrogen gas to recover deepheavy oil and/or hydrocarbons from the formation and reservoirs thatconventional steam injection processes and compositions are unable torecover.

According to certain embodiments of the invention, as steam is generateddownhole, heat delivery efficiency is maximized and heat loss due tounder and/or overburdens is minimized compared to conventional steaminjection processes and compositions. Furthermore, various embodimentsof the invention provide a low cost method for delivering thermal energyto the formation and reservoirs to increase formation and reservoirtemperature, respectively, improve oil mobility, and achieve high heavyoil and hydrocarbon recovery.

Accordingly, in accordance with one embodiment, there is provided anenhanced oil recovery method for recovery of oil from a heavy oilformation, a deep oil reservoir, or a tight oil reservoir. The enhancedoil recovery method includes injecting, into one of the formation andthe reservoir, an aqueous composition including an ammonium containingcompound and a nitrite containing compound. The method further includesinjecting, into the one of the formation and the reservoir, anactivator. The activator initiates a reaction between the ammoniumcontaining compound and the nitrite containing compound, such that thereaction generates steam and nitrogen gas, increasing localized pressureand improving oil mobility, in the one of the formation and thereservoir, thereby enhancing oil recovery from the one of the formationand the reservoir.

In accordance with another embodiment, there is provided an oil wellstimulation composition, which includes an ammonium containing compound,a nitrite containing compound, and an activator. The activator initiatesa reaction between the ammonium containing compound and the nitritecontaining compound, such that the reaction generates steam and nitrogengas, increasing localized pressure and improving oil mobility, in theone of the formation and the reservoir, thereby enhancing oil recoveryfrom the one of the formation and the reservoir.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the invention arebetter understood with regard to the following Detailed Description,appended Claims, and accompanying Figures. It is to be noted, however,that the Figures illustrate only various embodiments of the inventionand are therefore not to be considered limiting of the invention's scopeas it may include other effective embodiments as well.

FIG. 1 is a schematic diagram of an enhanced oil recovery process, inaccordance with an embodiment of the invention.

FIG. 2 is a graph showing a thermodynamic profile of an exothermic redoxreaction of sodium nitrite and ammonium chloride for a reactor using theenhanced oil recovery process, as shown in FIG. 1, in accordance with anembodiment of the invention.

FIG. 3 is a graph showing an effect of the concentrations of reactantsin an aqueous composition, used for the enhanced oil recovery process,as shown in FIG. 1, on the temperature and pressure in a formation or areservoir due to an oxidation-reduction reaction, in accordance with anembodiment of the invention.

FIG. 4 is a graph showing the affected volume of recovered oil due tothe heat and steam generated downhole in a heavy oil formation, a deepoil reservoir, or a tight oil reservoir using the enhanced oil recoveryprocess, as shown in FIG. 1, in accordance with an embodiment of theinvention.

FIG. 5 is a graph showing a thermodynamic profile of an exothermicreaction to generate in-situ steam and nitrogen gas to enhance oilrecovery, in accordance with an embodiment of the invention.

FIG. 6 is a graph showing a pressure profile of an exothermic reactionto generate in-situ steam and nitrogen gas to enhance oil recovery, inaccordance with an embodiment of the invention.

DETAILED DESCRIPTION

The present invention will now be described more fully hereinafter withreference to the accompanying drawings, which illustrate embodiments ofthe invention. This invention may, however, be embodied in manydifferent forms and should not be construed as limited to theillustrated embodiments set forth herein. Rather, these embodiments areprovided so that this disclosure will be thorough and complete, and willfully convey the scope of the invention to those skilled in the art.Like numbers refer to like elements throughout. Prime notation, if used,indicates similar elements in alternative embodiments.

As generally mentioned above, embodiments of the invention relate to thestimulation of hydrocarbon-bearing, heavy oil containing formations,deep oil reservoirs, and tight oil reservoirs to enhance oil production.Various embodiments of the invention address problems associated withconventional steam injection processes, by providing methods andcompositions that utilize exothermic-reaction components to generatesteam and nitrogen gas downhole in a formation or reservoir to enhanceoil production, without the initial capital costs and injected heat lossat the pipelines that is commonly present with conventional steaminjection processes. The methods and compositions, according to variousembodiments of the invention, can greatly increase the production rateof oil from heavy oil containing formations, deep oil reservoirs, andtight oil reservoirs (i.e., low permeability formations and reservoirs),thus improving the economics of the development thereof.

As shown in FIG. 1, in accordance with an embodiment of the invention, amethod is provided for enhancing oil recovery from one of a formationand a reservoir. In accordance with certain embodiments, the formationincludes a hydrocarbon-bearing heavy oil formation, and the reservoirincludes one of a conventional oil reservoir, a heavy oil reservoir, adeep and shallow oil reservoir, an on-shore reservoir, an off-shorereservoir, a tar mat, and an oil sand. The method includes injecting, at100, into the formation or the reservoir, an aqueous compositionincluding an ammonium containing compound and a nitrite containingcompound. In at least one embodiment, the aqueous composition includes 1to 9M of an ammonium containing compound and 1 to 9M of a nitritecontaining compound. In a preferred embodiment, the aqueous compositionincludes 3 to 6M of an ammonium containing compound and 3 to 6M of anitrite containing compound. In certain embodiments, the aqueouscomposition includes a 1:1 ratio of the 1 to 9M of the ammoniumcontaining compound and the 1 to 9M of the nitrite containing compound.The concentration of the reactants in the aqueous compositioncorresponds directly to an increase in temperature and pressure in theformation or the reservoir due to an oxidation-reduction reaction, inaccordance with various embodiments as will be described in more detailbelow (see FIGS. 2 and 3), The aqueous composition takes advantage ofthe oxidation-reduction reaction (also referred to as a ReDoxcomposition) for the in-situ generation of steam and nitrogen gasdownhole in the formation or the reservoir, thereby creating an area ofhigh localized pressure. In accordance with one embodiment, 3M of theammonium containing compound and 3M of the nitrite containing compoundgenerated approximately 137,000 BTU/barrel of in-situ steam, as anon-limiting example. By creating this area of high localized pressurewithin the formation, for example, micro-fracturing of the nearby strataoccurs, thereby improving the permeability of the near fracture surfaceof the formation, and improving oil mobility, both of which facilitatehigh heavy oil and hydrocarbon recovery from the formation. The highlocalized pressure created in the reservoir similarly improves thepermeability of the reservoir and the oil mobility, both of whichfacilitate high heavy oil and hydrocarbon recovery from the reservoir.

The method further includes injecting, at 110, into the formation or thereservoir, up to 5 vol % (of the total volume) of a 0.1 to 1M activator.The activator initiates a reaction, at 120, between the ammoniumcontaining compound and the nitrite containing compound, such that thereaction generates steam and nitrogen gas downhole in the formation orthe reservoir for increasing the localized pressure in the formation orthe reservoir, and improving mobility of oil, at 130, in the formationor the reservoir, thereby enhancing recovery of the oil from theformation or the reservoir. In accordance with at least one embodiment,the reservoir temperature is less than or equal to 150° F. (65.5556° C.)(i.e., a temperature reservoir to activate the oxidation-reductionreaction using the activator).

The methods and composition, in accordance with certain embodiments,generate and release two types of energy—kinetic energy and thermalenergy, which is a result of the exothermic nature of theoxidation-reduction reaction. In accordance with one embodiment, anaqueous solution including an ammonium containing compound, for example,ammonium chloride (NH₄Cl) and a nitrite containing compound, forexample, sodium nitrate (NaNO₂), are mixed with an injection of anactivator, for example, an acid (H+), heat, or water (H+), wherebynitrogen gas (N₂), sodium chloride (NaCl), water, and heat are thebyproducts (see Equation [1]). In-situ steam is generated from the heatproduced by the oxidation-reduction reaction, and in conjunction withthe nitrogen gas, increases the localized pressure in the formation orthe reservoir, thereby enhancing oil mobility in the formation or thereservoir and hydrocarbon recovery therefrom.

For each of the embodiments described herein, exemplary ammoniumcontaining compounds include, for example, ammonium chloride, ammoniumbromide, ammonium nitrate, ammonium sulfate, ammonium carbonate, andammonium hydroxide.

For each of the embodiments described herein, exemplary nitritecontaining compounds include, for example, sodium nitrite, potassiumnitrite, sodium hypochlorite.

For each of the embodiments described herein, exemplary activatorsinclude, for example, weak acids, such as acetic acid, strong acids,such as hydrochloric acid, and dilute strong acids. In general, anycompound that is capable of releasing an acidic hydrogen can be used asan activator. In certain preferred embodiments, acetic acid is used asthe activator. In certain embodiments, a 0.1 M solution of acetic acidhaving a concentration of about 0.5 vol % (of the total volume) isutilized. In certain embodiments, dilute strong acids, such as diluteHC1, is utilized to activate the oxidation-reduction reaction, with orwithout the addition of a buffer. One main advantage of the utilizationof dilute strong acids is the increased control over the reaction.

In various embodiments, the temperature within the formation or thereservoir is sufficient to serve as the activator or co-activator (alongwith the acid or other hydrogen-releasing compound) to activate thereaction between the components of the aqueous composition, while inother embodiments additional amounts of heat are supplied to theformation or the reservoir. For example, in certain embodiments, thetemperature within the formation or the reservoir is about 90° C. orhigher, alternatively at least about 70° C., and alternatively at leastabout 60° C. In some embodiments, the temperature within the formationor the reservoir is between about 60 to 70° C., and alternativelybetween 65° C. to 80° C. In a preferred embodiment, the temperature inthe formation or the reservoir is at least 45° C., the temperature atwhich the oxidation-reaction in the formation or the reservoir isactivated.

As noted above, in certain embodiments where the temperature of theformation or the reservoir is used to activate or initiate theoxidation-reduction reaction, a buffer is employed, such that the acidichydrogen ions are slowly released. The buffer includes ethyl acetate, asa non-limiting example. In accordance with certain embodiments, thebuffer is employed in the formation or the reservoir at a temperature ofless than 75° C.

Exemplary combinations of reactants for the aqueous composition include,for example, urea and sodium hypochlorite, urea and sodium nitrite,ammonium hydroxide and sodium hypochlorite, ammonium chloride and sodiumnitrite, and sodium nitrite and ammonium nitrate.

In certain embodiments, the aqueous composition includes equimolaramounts of the ammonium containing compound and the nitrite containingcompound when they are supplied to the formation or the reservoir toensure complete reaction of both components. In alternate embodiments,up to about a 5% excess of either component can be employed; however, itis generally preferred that equimolar amounts are employed. Thus, incertain embodiments, the ammonium containing compound and the nitritecontaining compound are provided in a ratio ranging from between about1.1:1 to 1:1.1, alternatively between about 1.05:1 and 1:1.05, andalternatively about 1:1.

In certain embodiments, the reaction between the ammonium containingcompound and the nitrite containing compound in the presence of theactivator results in the local generation of about 60 L of nitrogen gasper one liter of reactants and about 225 Kcal (942.03 kJ) of heat perone liter of reactants. In certain embodiments, the reaction of theammonium containing compound and the nitrite containing compound in thepresence of the activator results in the generation of at least about 50Kcal (209.34 kJ) of heat per one liter of reactants, alternatively atleast about 100 Kcal (418.68 kJ) of heat per one liter of reactants,alternatively at least about 150 Kcal (628.02 kJ) of heat per one literof reactants, and alternatively at least about 200 Kcal (837.36 kJ) ofheat per one liter of reactants.

In various embodiments, the heat generated from the oxidation-reductionreaction generates at least about 15 times the required heat to vaporizewater downhole in the formation or the reservoir. For example, inaccordance with certain embodiments, the downhole temperature isincreased by at least about 50° C., alternatively by at least about 75°C., and alternatively by at least about 100° C.

In certain embodiments, the method further includes injecting 0.1 to 1Mof a non-acidic well stimulation fluid, for example, sodium hydroxide(NaOH), which prevents a premature reaction between the ammoniumcontaining compound and the nitrite containing compound, therebyallowing the reactants to reach the formation or the reservoir beforethe high temperatures therewithin cause the reaction between thecomponents of the aqueous composition.

The in-situ generation of heat and nitrogen gas (and resulting increasein pressure within the formation at the reaction site), increases thepermeability of certain oil formations and reservoirs. For example, theheat and gas that are generated by the oxidation-reduction reactioncause tensile and thermal fractures within the hydraulically induced andwithin the existing fractures in the formation. It is understood thatthe generation of microfractures within the formation or the reservoirmay depend on the type of formation or reservoir being treated. This,coupled with the administration of the non-acidic well stimulation fluiddescribed above, results in the increased production of oil recoveryfrom the formation or the reservoir as both the aqueous composition andthe non-acidic well stimulation fluid act on the formation or thereservoir in a manner that results in increased permeability.

In certain embodiments, the ammonium containing compound and the nitritecontaining compound are injected into the formation or the reservoirapproximately 5 minutes before the injection of the non-acidic wellstimulation fluid, alternatively approximately 10 minutes before theinjection of the non-acidic well stimulation fluid, and alternativelyapproximately 15 minutes before the injection of the non-acidic wellstimulation fluid.

In certain embodiments, the inventive aqueous composition includes theammonium containing compound and the nitrite containing compound, one ofwhich is optionally encapsulated. The water and/or the heat of theformation or the reservoir facilitates the erosion of the encapsulatedcomponent, such that the reaction between the ammonium containingcompound and the nitrite containing compound is delayed, allowing theaqueous composition to migrate and seep into the fractures within theformation or the reservoir.

In certain embodiments, the ammonium containing compound or the nitritecontaining compound is optionally encapsulated with a binder to form asolid matrix with the component. Exemplary encapsulating bindersinclude, for example, 55-carboxymethyl cellulose and xanthan. Exemplarybinders are preferably reactive with water or the non-acidic wellstimulation fluid, and/or heat, such that upon contact with thenon-acidic well stimulation fluid or water, or upon heating, the bindererodes or dissolves, allowing the reactants of the aqueous compositionto react with one another downhole in the formation or the reservoir.

In certain embodiments, the ammonium containing compound or the nitritecontaining compound is optionally encapsulated with a polymer, forexample, a hydrated polymer. Exemplary polymers include, for example,guar, chitosan and polyvinyl alcohol. In certain embodiments, theaqueous composition optionally includes a buffer.

Example of an Estimation of Generated Heat Downhole:

FIG. 4 is a graph showing the affected volume of recovered oil due tothe heat and steam generated downhole in a heavy oil formation, a deepoil reservoir, or a tight oil reservoir using the enhanced oil recoveryprocess, as shown in FIG. 1, in accordance with an embodiment of theinvention. FIG. 4 shows that, when three barrels/min of one molar ofreactants are injected downhole in a formation or a reservoir at atemperature of about 140° F. and a pressure of about 4300 psi (29647.425kPa), assuming the formation or the reservoir porosity to be about 0.05vol % (of the total volume), the required heat to vaporize water in thereservoir is about 150 KW. The heat generated downhole from theexothermic oxidation-reduction reaction discussed above for variousembodiments is 2500 KW, which is 16 times the required heat to generatesteam. The overall affected volume from the heat and generated steamdownhole is estimated to be 4200 ft³/h (118.93 m3/h). This will scale upand down with concentration, and therefore a 2 M solution would release5.94 kg/s and so on.

These calculations are based around assumptions set out on pump flowrate in the paper by Marques, et al. “A New Technique to TroubleshootGas Hydrates Buildup Problems in Subsea Christmas Trees” SPE77572.

FIG. 5 is a graph showing a thermodynamic profile of an exothermicreaction to generate in-situ steam and nitrogen gas to enhance oilrecovery, in accordance with an embodiment of the invention. FIG. 5shows the generation of heat as a function of time for the reaction ofequimolar amounts of the ammonium containing compound (e.g., ammoniumchloride) and the nitrite containing compound (e.g., sodium nitrite). Asshown in FIG. 5, the temperature rises rapidly to a peak within about 10minutes of reaction, maintains an elevated temperature for approximately20 minutes, and slowly cools over the next 30 minutes. FIG. 5 provides aproof of concept that the temperature increases as a result of theexothermic oxidation-reduction reaction and that the reaction may bedesigned to reach a required temperature, such that thermal fracturesin, for example, the formation or the reservoir are created. Thethermodynamic results of the reaction show an increased temperature fromroom temperature up to 100° C. The generated temperature is a functionof reactants concentrations. In accordance with certain embodiments, thedownhole temperature in the formation or reservoir is increased by atleast about 50° C., alternatively by at least about 75° C., andalternatively by at least about 100° C.

FIG. 6 is a graph showing a pressure profile of an exothermic reactionto generate in-situ steam and nitrogen gas to enhance oil recovery, inaccordance with an embodiment of the invention. FIG. 6 shows the amountof pressure generated by the reaction of the ammonium containingcompound (e.g., ammonium chloride) and the nitrite containing compound(e.g., sodium nitrite). The test was run in a high temperature, highpressure (HT/HP) filter press apparatus. Prior to initiating thereaction, the HT/HP filter press apparatus was set at 200 psi (1378.95kPa). The reaction showed that the pressure gradually increased to about400 psi (2757.9 kPa) during the reaction. FIG. 6 further demonstratesthat the pressure increase experienced in the formation or the reservoiris due to the nitrogen gas generated as a result of theoxidation-reduction reaction, and is a function of reactantsconcentration.

Advantageously, in contrast to some conventional stimulation methods,the methods and compositions described herein do not produce anydamaging by-products as a result of the in-situ reaction. For example,the acids utilized as activators are typically consumed by theoxidation-reduction reaction and are only present in relatively smallquantities, such that there is little or no residual acid remaining thatmay cause environmental concerns. As a result, following the stimulationprocedure, no clean-up procedure is required.

The methods and compositions discussed herein solve several problemsthat are frequently encountered during the construction of commercialwells in deep oil and tight oil reservoirs.

First, problems associated with damage to the formation caused bycurrent hydraulic fracturing methods can be eliminated. For example, themethods and compositions described herein, advantageously help toeliminate fracturing-fluid filtrate that can be locked near a recentlycreated fracture surface by creating many tensile fractures near thefracture surface such that any filtrate readily flows through thesefractures toward the well.

Second, the methods and compositions provided herein, advantageouslyenhance production over traditional hydraulic fracturing methods throughthe creation of microfractures, which provide additional conductivity tothe near fracture surface, such that it provides new channels for gas toflow toward the created fracture. The additional reservoir volumecontacting the well contributes significantly to the overall flowefficiency of the drainage area being affected by the induced fracture.

Finally, current hydraulic fracturing techniques that require manyfracturing stages to create sufficient reservoir volume contact withinthe well to be commercial are eliminated as a result of the productionof microfractures due to the gas and heat that are produced. By reducingthe number of required fracturing stages for production, the presentstimulation treatment described herein is both more cost effective andcompleted more quickly, thereby providing viable economical options forthe stimulation of low producing wells.

The present invention may suitably comprise, consist or consistessentially of the elements disclosed and may be practiced in theabsence of an element not disclosed. For example, it can be recognizedby those skilled in the art that certain steps can be combined into asingle step.

Unless defined otherwise, all technical and scientific terms used havethe same meaning as commonly understood by one of ordinary skill in theart to which this invention belongs.

The singular forms “an,” and “the” include plural referents, unless thecontext clearly dictates otherwise.

As used herein and in the appended claims, the words “comprise,” “has,”and “include” and all grammatical variations thereof are each intendedto have an open, non-limiting meaning that does not exclude additionalelements or steps.

“Optionally” means that the subsequently described event orcircumstances may or may not occur. The description includes instanceswhere the event or circumstance occurs and instances where it does notoccur.

Ranges may be expressed herein as from about one particular value,and/or to about another particular value. When such a range isexpressed, it is to be understood that another embodiment is from theone particular value and/or to the other particular value, along withall combinations within said range.

Although the present invention has been described in detail, it shouldbe understood that various changes, substitutions, and alterations canbe made hereupon without departing from the principle and scope of theinvention. Accordingly, the scope of the present invention should bedetermined by the following claims and their appropriate legalequivalents.

What is claimed is:
 1. An oil well stimulation method for enhancing oilrecovery from one of a formation and a reservoir, the oil wellstimulation method comprising: designing an aqueous composition to reacha required temperature, the required temperature sufficient to formthermal fractures within hydraulically induced and existing fractures inthe formation or reservoir, where reaching the required temperature is afunction of concentration of reactants in the aqueous composition;injecting, at an injector disposed a distance away from an oil producer,into the formation or reservoir, the aqueous composition, the aqueouscomposition comprising an ammonium containing compound and a nitritecontaining compound; injecting, at the injector, into the formation orreservoir, an activator comprising an acidic hydrogen compound includingone of a weak acid, a strong acid, and a dilute strong acid, theactivator initiating a reaction between the ammonium containing compoundand the nitrite containing compound, such that the reaction generatessteam in situ and generates nitrogen gas in situ, increasing localizedpressure, wherein the activator is consumed by the reaction such that noresidual activator remains to cause environmental concerns; generatingmicrofractures, including tensile and thermal fractures, within theformation or reservoir creating additional reservoir volume; andimproving oil mobility, in the formation or reservoir, by the steam andnitrogen gas generated in situ, thereby enhancing oil recovery from theformation or reservoir at the oil producer, without requiring a clean-upprocedure for any residual acid from unreacted activator after the oilwell stimulation method.
 2. The oil well stimulation method as definedin claim 1, wherein the aqueous composition comprises a compoundselected from the group consisting of: ammonium chloride, ammoniumbromide, ammonium nitrate, ammonium sulfate, ammonium carbonate, andammonium hydroxide.
 3. The oil well stimulation method as defined inclaim 1, wherein the aqueous composition comprises a compound selectedfrom the group consisting of: sodium nitrite, potassium nitrite, andsodium hypochlorite.
 4. The oil well stimulation method as defined inclaim 1, wherein the step of injecting the activator comprises injectingthe dilute strong acid.
 5. The oil well stimulation method as defined inclaim 1, wherein the step of injecting the aqueous composition comprisesinjecting equimolar amounts of the ammonium containing compound and thenitrite containing compound.
 6. The oil well stimulation method asdefined in claim 1, further comprising the step of: injecting, into theformation or reservoir, a non-acidic well stimulation fluid, thenon-acidic well stimulation fluid being operable to delay the reactionbetween the ammonium containing compound and the nitrite containingcompound.
 7. The oil well stimulation method as defined in claim 1,wherein the step of injecting the aqueous composition comprisesinjecting 1 to 9 molar of the ammonium containing compound and 1 to 9molar of the nitrite containing compound.
 8. The oil well stimulationmethod as defined in claim 7, wherein the step of injecting the aqueouscomposition comprises injecting 3 to 6 molar of the ammonium containingcompound and 3 to 6 molar of the nitrite containing compound.
 9. The oilwell stimulation method as defined in claim 1, wherein the step ofinjecting the activator is performed without the addition of a buffer.10. The oil well stimulation method as defined in claim 1, wherein thestep of generating microfractures occurs by a pressure increase due tonitrogen release within about 60 minutes of injecting the activator. 11.The oil well stimulation method as defined in claim 6, wherein thenon-acidic well stimulation fluid comprises sodium hydroxide.
 12. Theoil well stimulation method as defined in claim 11, wherein thenon-acidic well stimulation fluid is injected into the formation orreservoir between about 5 minutes and about 15 minutes after theammonium containing compound and the nitrite containing compound areinjected into the formation or reservoir.
 13. The oil well stimulationmethod as defined in claim 1, further comprising the step ofencapsulating the ammonium containing compound or the nitrite containingcompound.
 14. The oil well stimulation method as defined in claim 13,wherein the step of encapsulating utilizes a compound selected from thegroup consisting of: binder and polymer.
 15. The oil well stimulationmethod as defined in claim 1, wherein the heat generated from thereaction between the ammonium containing compound and the nitritecontaining compound is at least about 15 times the heat required tovaporize water downhole in the formation or reservoir.
 16. The oil wellstimulation method as defined in claim 1, wherein the heat generatedfrom the reaction between the ammonium containing compound and thenitrite containing compound is sufficient to increase localized downholetemperature by at least about 50° C.
 17. The oil well stimulation methodas defined in claim 1, wherein the heat generated from the reactionbetween the ammonium containing compound and the nitrite containingcompound is sufficient to increase localized downhole temperature by atleast about 75° C.
 18. The oil well stimulation method as defined inclaim 1, wherein the heat generated from the reaction between theammonium containing compound and the nitrite containing compound issufficient to increase localized downhole temperature by at least about100° C.
 19. The oil well stimulation method as defined in claim 1,wherein the required temperature is reached within about 10 minutes ofthe reaction, and further comprising the step of maintaining an elevatedtemperature within the formation or reservoir for at least about 20minutes before the formation or reservoir cools for about 30 minutes.